EP1317512B1 - Bisazo dyestuffs based on hydroxynaphthalene carboxylic acid - Google Patents

Description

The invention relates to bisazo dyes based on hydroxynaphthalene carboxylic acid, Colorants containing these bisazo dyes included and the use of bisazo dyes for dyeing natural and synthetic materials.

Bisazo dyes are a technically important class of dyes and numerous dyes of this type have been developed.

DE 198 15 945 A 1 discloses cationic sulfonic acid dyes, in which a hydroxy-aminonaphthalene sulfonic acid is attached to two phenyl radicals, each have a substituent with a quaternary nitrogen atom wear, is azo-coupled.

DE 1 768 892 A describes bisazo dyes in which two are used Amide bonds linked hydroxynaphthalene carboxylic acid residues in each case are azo coupled to doubly substituted phenyl groups.

in der

A

Amido, Thioharnstoff, Alkylendiamid, Phenylendiamid, Disulfid, Azo, Imino, Carbonyl oder Sulfonyl bedeutet.

DE 2 246 495 A discloses bisazo dyes based on hydroxynaphthalene carboxamides. Two hydroxynaphthalene carboxamide groups are connected via azo bridges to an aromatic, for example a substituted or unsubstituted compound of the type

in the

A

Amido, thiourea, alkylenediamide, phenylenediamide, disulfide, azo, imino, carbonyl or sulfonyl.

verbunden, wobei Y für eine direkte Bindung, gegebenenfalls substituiertes Alkylen, -S-, -O-, -NH-CO-NH- oder -CH=CH- steht.US-A-4,046,502, DE 2 061 964 A and CH 554 399 disclose nonionic, monocationic and dicationic bisazo dyes based on hydroxynaphthalene carboxamides. Here are hydroxynaphthalene carboxamide residues via azo bridges with a compound of the type

connected, where Y is a direct bond, optionally substituted alkylene, -S-, -O-, -NH-CO-NH- or -CH = CH-.

The known dyes are lightfast and Brilliance unsatisfactory. There is therefore the task to provide further, improved dyes that have good light fastness and brilliance at the same time.

Surprisingly, it has now been found that the compounds de Formulas Ia and Ib given below solve this problem.

oder der Formel Ib,

worin

R¹

Wasserstoff oder Methyl ist,

die Gruppen X unabhängig voneinander für -CH₂CH₂- oder -CH₂CH₂CH₂stehen,

R²,

R³, R⁴ unabhängig voneinander für Wasserstoff oder Methyl stehen,

A

ein Anion ist, und

n

der Wertigkeit von A entspricht.

The present invention thus relates to bisazo compounds of the formula Ia

or the formula Ib,

wherein

R ¹

Is hydrogen or methyl,

the groups X independently of one another represent -CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ ,

R ² ,

R ³ , R ⁴ independently of one another represent hydrogen or methyl,

A

is an anion, and

n

corresponds to the valency of A.

The present invention also relates to colorants, the at least one compound of formula I and optionally other cationic, nonionic or anionic dyes and / or Contain auxiliaries and / or carriers.

The present invention also relates to the use of the compounds of formula I for dyeing, padding or printing of natural or synthetic polymeric material, Paper materials, leather, natural and synthetic fiber materials.

The bisazo compounds according to the invention are derivatives of 2-hydroxynaphthalene-3-carboxylic acid (Bon-acid).

In the bisazo compounds according to the invention, groups X be the same or different, preferably they are the same.

The groups NR ² R ³ or NR ² R ³ R ⁴ can also be the same or different, but they are preferably the same. Fully symmetrical bisazo compounds are particularly preferred.

NR ² R ³ stands in particular for

NR ² R ³ R ⁴ stands in particular for

In the case of the cationic bisazo compounds of the formula Ib Charge balancing anions A⊖ required. Inorganic ones are suitable and organic anions, e.g. B. fluoride, chloride, bromide, iodide, Sulfate, methyl sulfate, phosphate, anions of carboxylic acids or sulfonic acids, such as formate, acetate, propionate, mono-, dioder Trichloroacetate, lactate, methoxyacetate, citrate, succinate, methanesulfonate, Benzenesulfonate, 2- or 4-methylbenzenesulfonate or Naphthalene sulfonate.

und anschließende Azokupplung mit einer Verbindung der Formel III

gefolgt von Quarternisierung, oder alternativ durch Quarternisierung der Kupplungskomponente der Formel IV

und anschließender Azokupplung in geeigneten Molverhältnissen. Die Reste X, R¹, R² und R³ haben dabei die vorstehend angegebenen Bedeutungen.The compounds according to the invention can be prepared by the processes described in DE 2061964. They can preferably be prepared by diazotization of the compound of the formula II

and then azo coupling with a compound of formula III

followed by quaternization, or alternatively by quaternization of the coupling component of formula IV

and subsequent azo coupling in suitable molar ratios. The radicals X, R ¹ , R ² and R ³ have the meanings given above.

The quaternization is carried out, for example, by reacting a compound of the formula IV with R ⁴ -A, where R ⁴ and A have the meanings given above. Examples of R ⁴ -A are methyl iodide or dimethyl sulfate.

Diazotization, azo coupling, quaternization and condensation are processes known per se and can be carried out according to the usual Standard methods are carried out.

The invention also relates to colorants which contain the invention Connections included. They are generally in one Amount in the range of 0.1 to 20 wt .-%, based on the total weight of the colorant.

The bisazo compounds according to the invention can on their own in mixtures with one another or together with other cationic ones or anionic compounds in the form of a solution or in the form of powders or granules are used, d. that is, they are very easy to combine. The processing z. B. in stable, liquid or solid colorants can be carried out in a known manner, z. B. by grinding or granulating or by dissolving in suitable Solvents, optionally with the addition of auxiliaries, z. B. a stabilizer.

The colorants are preferably in aqueous solution. You can usual auxiliaries, such as wetting agents, thickeners, with Contain water-miscible organic solvents etc. preferred Thickeners are polymers such as polyacrylic acids, polyacrylic acid derivatives, Polyvinylamines, polyvinylamides, polyvinyl acetates, Polyvinyl alcohols, polyvinyl pyrrolidones, polysiloxanes or Copolymers thereof. Likewise, oligomers of ethyleneimine, Ethylene oxide or propylene oxide or derivatives of these oligomers come into use.

The bisazo compounds according to the invention are suitable for dyeing, Padding and printing on various materials, in particular of paper and paper materials, cellulose, cotton, Leather, bast fibers, hemp, flax, sisal, jute, coconut or straw. They are particularly suitable for dyeing, padding and printing of acrylonitrile polymer and acrylonitrile interpolymer fibers, - threads and textiles made from them, from synthetic, amides and polyesters modified by anionic groups, of various mixed fabrics, plastic and natural resin materials. They are also well suited for, for example Printing and painting inks as well as for inkjet inks.

The compounds can preferably be used as dyes in the preparation of dyed, glued and unsized in the mass Paper. You can also use it to dye paper applied after the immersion process.

The dyeing, padding and printing takes place according to known Method.

The bisazo compounds according to the invention are notable for easy accessibility and applicability as dyes for one wide variety of different materials, as well as superior dye properties.

The new dyes dye the wastewater in paper production practically no or little at all for what to keep clean the water is particularly advantageous. They are highly substantive do not mottle when colored on paper and are largely pH-insensitive. Especially the dyeings on paper, but also on other materials are characterized by good Lightfastness. The nuance changes after long exposure Tone in tone.

The colored papers, which have good bleachability, are wet-fast, not only against water, but also against milk, Soapy water, sodium chloride solutions, fruit juices and sweetened mineral water. Because of their good alcohol fastness, they are also against alcoholic beverages resistant.

Especially for paper for household purposes and other purposes, where it is foreseeable that the colored paper in wet Condition with other objects, e.g. B. textiles in contact resistance to bleeding is extremely important. For the Paper industry, papers and colored paper pulp are very important which can be easily bleached so that they can be reprocessed or can be used immediately for other types of paper can. The bisazo compounds according to the invention are outstandingly suitable for these purposes.

Of particular note are their good migration, Fastness to heat, light and weather, the pure colors and the high color strength.

The invention is illustrated below using examples which In no way limit the invention, explained in more detail.

example 1

4.24 g (0.02 mol) of 4,4'-diaminodibenzyl (= 1,2-di- (4-aminophenyl) ethane) were suspended in 100 ml of water and dissolved by adding 12 ml of concentrated hydrochloric acid. The solution was cooled to 0 ° C. and 13.2 ml of a 30% sodium nitrite solution were added. After a diazotization time of 45 minutes at 0 to 5 ° C, the excess nitrite was decomposed by adding about 0.2 g of amidosulfonic acid. The solution of the diazo component thus prepared was turned into a suspension of 10.9 g (0.04 mol) of 2-hydroxy-3- (3- (N, N-dimethylamino) propyl) naphthamide in cooled to 0 ° C. within 30 minutes 300 ml of water dropped. The mixture was left to stir at 5 ° C. for one hour. During this time, the pH was kept at 8 to 9 with 20% sodium hydroxide solution. The pH was then adjusted to 11 by adding a further 20% sodium hydroxide solution and the dye was isolated by filtration. After drying, 13.94 g (89.5% of theory) of a red dye with the formula:

A sample recrystallized from ethyl acetate / ethanol provided the following spectroscopic data:
UV / Vis spectrum (methanol / acetic acid in a volume ratio of 9: 1): λ _max = 536 nm

The following dyes were prepared analogously to Example 1

bestimmt. Die Ergebnisse sind in der nachfolgenden Tabelle 1 angegeben. Verbindung Lichtechtheit A 1-2 B 1-2 C < 1 D < 1 The light fastness of these compounds was determined according to DIN ISO 105 B 02 in comparison to compounds of the formula

certainly. The results are shown in Table 1 below. connection fastness A 1-2 B 1-2 C <1 D <1

It can be seen that the compounds A and B surprisingly have significantly better light fastness than the compounds C and D of DE 2061964. In addition it was found that the compounds A and B in contrast to the Compounds C and D with drinking water show no cloudiness.

Claims (4)

1. Bisazo compounds of the formula Ia or Ib

   

   

   where

   R¹

   is hydrogen or methyl,

   the X groups are independently -CH₂CH₂- or -CH₂CH₂CH₂-,

   R², R³, and R⁴

   are independently hydrogen or methyl,

   A

   is an anion and

   n

   corresponds to the valency of A.

2. Bisazo compounds as claimed in claim 1, of the following formulae

   

   
3. A colorant containing at least one compound of the formula I as per claim 1 or 2 and optionally further cationic or anionic or nonionic dyes and/or assistants.
4. The use of the bisazo compounds of the formula I as per claim 1 or 2 for dyeing, padding or printing paper, paper materials, cellulose, cotton, leather and natural and synthetic fibers or fiber materials.